EP0131354A1

EP0131354A1 - Alkylsulfonium salts of N-phosphonomethylglycine

Info

Publication number: EP0131354A1
Application number: EP84303080A
Authority: EP
Inventors: Michael Paul Prisbylla
Original assignee: Stauffer Chemical Co
Current assignee: Stauffer Chemical Co
Priority date: 1983-05-12
Filing date: 1984-05-08
Publication date: 1985-01-16
Also published as: IN160707B; DK230484A; US4464194A; ES8505806A1; DD220220A5; HUT34675A; ZA843567B; BR8402256A; ES532414A0; JPS59212498A; CA1228866A; AU560037B2; PL137841B1; DK230484D0; KR840009312A; PH20412A; CS241084B2; AU2793784A; IL71811A0; RO90109A

Abstract

As a new compound, mixed alkylsulfonium salts of N-phosphonomethylglycine having the formula

wherein R' is selected from the group consisting of long-chain saturated or unsaturated alkyl groups having from 12 to 20 carbon atoms and R² and R₃ are the same or different and are selected from the group consisting of lower alkyl having from 1-3 carbon atoms.

Description

Background of the Invention

This invention relates to mixed alkylsulfonium salts of N-phosphonomethylglycine, compounds which have been found to be effective herbicide and plant growth regulators.
Herbicides are widely used by farmers, commercial agricultural conpanies, and other industries in order to increase crop yields for such staple crops as corn, soybeans, rice, and the like, and to eliminate weed growth along highways, railroad rights-of-way, and other areas. Herbicides are effective in killing or controlling unwanted weeds which compete for soil nutrients with the crop plants, and by reason of the fact that they kill weeds, are responsible for improving the aesthetic appearance of highway and railroad rights-of-way. There are a number of different types of herbicides presently sold commercially, and these fall into two general categories. The categories are pre-emergence and post-emergence herbicides. The pre-emergence herbicides are normally incorporated into the soil prior to the emergence of the weed plants from the soil, and the post-emergence herbicides are normally applied to plant surfaces after emergence of the weeds or other unwanted plants from the soil.
One of the earliest post-etnergence herbicides used commercially was 2,4-D (2,4-dichlorophenoxyacetic acid). After a number of years of use of this and similar compounds such as 2,4,5-T (2,4,5-trichlorophenoxy acetic acid), it was found that certain decomposition products of these herbicides were long lasting and were not biodegradable. While there has been some dispute between governmental agencies and commercial interests regarding the effects of residual products of 2,4-D, 2,4,5-T and similar compounds, the agencies nevertheless restricted the use of these herbicides in the United States some years ago. Since that time, efforts have been made to develop herbicides which are biodegradable into harmless residues within a relatively short time after their application.
One such canpound, which has been found to be biodegradable, yet which is effective as a herbicide and plant growth regulator when employed at lower rates, is N-phosphonocnethylglycine and various salts thereof. The N-phosphonanethylglycine and certain agriculturally effective salts have been approved for use by the U.S. Government, and, as a consequence, this herbicide has become commercially successful.
The N-phosphonomethylglycine and certain salts are the only effective and approved post-emergence herbicides in the field. The present commercial compound is the isopropylamine salt of N-phosphonomethylglycine and derivatives thereof.
In field use it is normally applied in amounts of from 0.01 to about 20 pounds per acre, preferably from 2 to 6 pounds per acre.

THE PRIOR ART

The N-phosphonomethylglycines, and certain soluble salts thereof, can be made in a number of different ways. One such method, as described in U.S. Patent 3,160,632 (Tby et al., December 8, 1964) is to react N-phosphinomethylglycine (glycinemethylenephosphinic acid) with mercuric chloride in a water solvent at reflux temperature, and subsequently separating the reaction products. Other methods include the reaction of ethyl glycinate with formaldehyde and diethylphosphite. The latter method is described in U.S. Patent No. 3,799,758 (Franz, March 26, 1974). In addition, there is a whole series of patents, relating to N-phosphonomethylglycines, their salts, and derivatives thereof, described as being useful herbicides and plant growth regulators. Such additional patents relating to the N-phosphonomethylglycines, methods of application, methods of preparation, salts, and derivatives, include U.S. Patent 3,868,407, U.S. Patent 4,197,254, and U.S. Patent 4,199,354, among others.
Specific salts of N-phosphonanethylglycine which have been found to be herbicidally effective are the sulfonium. and sulfoxonium salts.
Other salts are constantly being sought which are more economically and agriculturally efficient or cost effective than those previously known, or are easier to produce.

Description of the Invention

It has now been discovered that certain new and novel mixed alkylsulfonium salts of N-phosphonomethylglycine have good herbicidal and plant growth regulating activity.
The mixed alkylsulfonium salts of N-phosphonomethylglycine which are the subject of this invention have the formula
wherein R¹ is selected from the group consisting of long-chain saturated or unsaturated alkyl groups having from 12 to 20 carbon atoms and R² and R₃ are the same or different and are selected from the group consisting of lower alkyl having from 1-3 carbon atoms.
Representative salts falling within the scope of the generic formula indicated above include the dimethyloctadecyl sulfonium salt of N-phosphonomethylglcyine, the dimethylhexadecyl sulfonium salt of N-phosphonomethylglycine, the dimethyltetradecyl sulfonium salt of N-phosphonomethylglycine and the dimethyldodecyl sulfonium salt of N-phosphonomethylglycine.
All of the above-described salts can be produced by reacting N-phosphonomethylglycine with an appropriate alkylsulfoniun halide in the presence of silver oxide and filtering the insoluble silver halide precipitated as a consequence of the reaction, leaving the alkylsulfoniumm salt of N-phosphonomethylglycine in solution.
In producing the compounds of the invention, the mixed alkylsulfoniun halide and the N-phosphonomethylglycine are first placed in a reaction vessel, and the silver oxide is thereafter admixed therewith incrementally.
The ratio of mixed alkylsulfonium halide to N-phosphonomethylglycine can range fran about 1 to about 1 mole. Sufficient silver oxide must be used to cause precipitation of the silver halide.
Preferred alkylsulfonium halides used to produce the compounds of the invention include dimethyloctadecyl sulfonium iodide.
N-phosphonanethylglycine is a known compound and can be produced as described in U.S. Patent 3,160,632, Toy or can be purchased commercially from the Monsanto Company, St. Louis, Missouri.
The function of the silver oxide is to convert the N-phosphonomethylglycine to an anion form, with the concommitant precipitation of silver halide from the solution, thus leaving in solution the anionic N-phosphonomethylglycine and the cationic alkylphosphonium ion.
This invention will be more fully understood by reference to the following examples.

EXAMPLE 1

Preparation of Dimethyloctadecylsulfonium salt of N-Phosphonomethylqlycine

A round-bottan flask was obtained, and into this flask was charged 5.3 grams (g) (0.01 mole) of dimethyloctadecylsulfonium iodide and 1.0 g (0.01 mole) of N-phosphonomethylglycine in 130 milliliters (ml) of anhydrous methanol. Five-tenth grams of deionized water was then added, followed by 2.8 g (0.01 mole) of silver oxide in portions over a 30 minute time period.
After the silver oxide addition was completed, the solution was stirred rapidly for 2 hours at 25°C. The solution was thereafter filtered and the filter cake was washed with methanol. The filtrate was then vacuum stripped, yielding 2.8 g of a white solid having a decomposition point of about 130°C, and which was identified by nuclear mass resonance (NMR) and infrared (IR) techniques as being the dimethyloctadecylsulfonium salt of N-phosphonomethylglcyine.
The other compounds of the invention can be produced in a substantially similar manner by reacting an appropriate alkylsulfonium halide with N-phosphonomethylglycine in the presence of a silver oxide catalyst.
The herbicidal activity of the compounds of the invention is exhibited by means of tests in accordance with the following procedure.

EXAMPLE 2

Herbicidal Activity Tests

This example offers herbicidal activity test data to show the effectiveness of the alkylmethylammonium salt. The effect is observed by comparing the extent of weed control in test flats treated with the salt against that occurring in similar control flats. The soil used in these tests was a sandy loam soil from the Livermore, California area.
Also added to the soil was 17-17-17 fertilizer (N P₂O₅K₂O on a weight basis), amounting to 50 ppn by weight with respect to the soil, and 100 ppm Captan, a soil fungicide.
The treated soil was then placed in flats which were 3 inches deep, 6 inches wide, and 10 inches long. The soil was tamped and leveled with a row marker to impress six rows across the width of the flat. The test weeds were as follows:
Sufficient seeds were planted to produce several seedlings per inch in each row. The flats were then placed in a greenhouse maintained at 70 to 85°F (21 to 30°C) and watered daily by sprinkler.
Chemical application is made by spraying 12 days after planting. The spray solution is prepared by dissolvinq 60 mg of herbicide compound in 20 ml of acetone containing 1% Tween® 20 (polyoxysorbitan monolaurate), then adding 20 ml of water to the resulting solution. The solution is sprayed at 80 gallong/acre, resulting in a 4 lb/acre rate of chemical application.
Approximately 12-14 days after treatment, the degree of weed control was estimated and recorded as percentage control compared to the growth of the same species in an untreated check flat of the same age. The rating scale ranges from 0 to 100%, where 0 equals no effect with plant growth equal to the untreated control, and 100 equals complete kill.
The results are listed in Table I below. It is clear that the compounds of this invention are effective herbicides.

METHODS OF APPLICATION

The herbicidal compositions of the present invention are useful in controlling the growth of undesirable vegetation by pre-emerqence or post-emergence application to the locus where control is desired, including pre-plant and post-plant soil incorporation as well as surface application. The compositions are qenerally embodied in formulations suitable for convenient application. Typical formulations contain additional ingredients or diluent carriers which are either inert or active. Examples of such ingredients or carriers are water, organic solvents, dust carriers, granular carriers, surface active agents, oil and water, water- oil emulsions, wetting agents, dispersinq agents, and emulsifyinq aqents. The herbicidal formulations generally take the form of dusts, emulsifiable concentrates, granules and pellets, or microcapsules.

A. DUSTS

Dusts are dense powder compositions which are intended for application in dry form. Dusts are characterized by their free-flowin^q and rapid settling properties so that they are not readily windborne to areas where their presence is not desired. They contain primarily an active material and a dense, free-flowing, solid carrier.
Their performance is sometimes aided by the inclusion of a wetting agent, and convenience in manufacture frequently demands the inclusion of an inert, absorptive grinding aid. For the dust compositions of this invention, the inert carrier may be either of vegetable or mineral origin, the wetting agent is preferably anionic or nonionic, and suitable absorptive grinding aids are of mineral origin.
Suitable classes of inert solid carriers for use in the dust compositions are those organic or inorganic powders which possess high bulk density and are very free-flowing. They are also characterized by low surface area and poor liquid absorptivity. Suitable grinding aids are natural clays, diatomaceous earths, and synthetic mineral fillers derived from silica or silicate. Among ionic and nonionic wetting agents, the most suitable are the members of the group known to the art as wetting agents and emulsifiers. Although solid agents are preferred because of ease of incorporation, some liquid nonionic aqents are also suitable in the dust formulations.
Preferred dust carriers are micaceous talcs, pyrophyllite, dense kaolin clays, tobacco dust and ground calciun phosphate rock.
Preferred grinding aids are attapulgite clay, diatomaceous silica, synthetic fine silica and synthetic calcium and magnesium silicates.
Most preferred wetting aqents are alkylbenzene and alkyl-naphthalene sulfonates, sulfated fatty alcohols, amines or acid amides, long chain acid esters of sodium isothionate, esters of sodium sulfosuccinate, sulfated or sulfonated fatty acid esters, petroleun sulfonates, sulfonated vegetable oils, and ditertiary acetylenic glycols. Preferred dispersants are methyl cellulose, polyvinyl alcohol, lignin sulfonates, polymeric alkylnaphthalene sulfonates, sodium naphthalenesulfonate, polymethylene alkylnaphthalene sulfonates, sodium naphthalenesulfonate, polymethylene bisnaphthalenesulfonate, and sodium-N-mthyl-N-(lonq chain acid) taurates.
The inert solid carriers in the dusts of this invention are usually present in concentrations of from about 30 to 90 weight percent of the total composition. The grinding aid will usually constitute 5 to 50 weight percent of the compositions, and the waiting agent will constitute from about 0 to 1.0 weight percent of the composition. Dust compositions can also contain other surfactants such as dispersing agents in concentrations of up to about 0.5 weight percent, and minor amounts of anticaking and antistatic agents. The particle size of the carrier is usually in the range of 30 to 50 microns.

B. EMULSIFIABLE CONCENTRATES

Emulsifiable concentrates are usually solutions of the active materials in nonwater-miscible solvents together with an emulsifying agent. Prior to use, the concentrate is diluted with water to form a suspended emulsion of solvent droplets.
Typical solvents for use in emulsifiable concentrates include weed oils, chlorinated hydrocarbons, and nonwater-miscible ethers, esters, and ketones.
Typical emulsifying a^qents are anionic or nonionic surfactants, or mixtures of the two. Examples include long-chain alkyl or mercaptan polyethoxy alcohols, alkylaryl polyethoxy alcohols, sorbitan fatty acid esters, polyoxyethylene ethers with sorbitan fatty acid esters, polyoxyethylene glycol esters with fatty or rosin acids, fatty alkylol amide condensates, calcium and amine salts of fatty alcohol sulfates, oil soluble petroleum sulfonates, or preferably mixtures of these emulsifying agents. Such emulsifying agents will comprise fran about 1 to 10 weiqht percent of the total composition.
Thus, emulsifiable concentrates of the present invention will consist of from about 15 to about 50 weight percent active material, about 40 to 82 weight percent solvent, and about 1 to 10 weight percent emulsifier. Other additives such as spreading agents and stickers can also be included.

C. GRANULES AND PELLETS

Granules and pellets are physically stable, particulate compositions containing the active ingredients adhering to or distributed through a basic matrix of a coherent, inert carrier with macroscopic dimensions. A typical particle is about 1 to 2 millimeters in diameter. Surfactants are often present to aid in leaching of the active inqredient from the granule or pellet.
The carrier is preferably of mineral origin, and generally falls within one of two types. The first are porous, absorptive, preformed granules, such as preformed and screened granular attapulgite or heat expanded, granular, screened vermiculite. On either of these, a solution of the active agent can be sprayed and will be absorbed at concentrations up to 25 weight percent of the total weight. The second, which are also suitable for pellets, are initially powdered kaolin clays, hydrated attapulgite, or bentonite clays in the form of sodium, calcium, or magnesium bentonites. Water-soluble salts, such as sodium salts, may also be present to aid in the disintegration of granules or pellets in the presence of moisture. These inqredients are blended with the active components to give mixtures that are granulated or pelleted, followed by dryinq, to yield formulations with the active component distributed uniformly throughout the mass. Such qranules and pellets can also be made with 25 to 30 weight percent active component, but more frequently a concentration of about 10 weight percent is desired for optimum distribution. The qranular compositions of this invention are most useful in a size range of 15-30 mesh.
i The surfactant is generally a common wetting agent of anionic or nonionic character. The most suitable wetting agents depend upon the type of granule used. When preformed granules are sprayed with active material in liquid form the most suitable wetting agents are nonionic, liquid wetters miscible with the solvent. These are compounds most generally ) known in the art as emulsifiers, and comprise alkylaryl polyether alcohols, alkyl polyether alcohols, polyoxyethylene sorbitan fatty acid esters, polyethylene glycol esters with fatty or rosin acids, fatty alkylol amide condensates, oil solution petroleum or vegetable oil sulfonates, or mixtures of these. Such agents will usually comprise up to about 5 weiqht percent of the total composition.
When the active inqredient is first mixed with a powdered carrier and subsequently qranulated, or pelleted, liquid nonionic otters can still be used, but it is usually preferable to incorporate at the mixing stage one of the solid, powdered anionic wetting agents such as those previously listed for the wettable powders. Such agents will comprise from about 0 to 2 weight percent of the total composition.
Thus, the preferred qranular or pelleted formulations of this invention comprise about 5 to 30 percent by weight active material, about 0 to 5 weight percent wetting agent, and about 65 to 95 weiqht percent inert material carrier, as these terms are used herein.

D. MICROCAPSULES

Microcapsules consist of fully enclosed droplets or granules containing the active materials, in which the enclosing material is an inert porous membrane, arranged to allow escape of the enclosed materials to the surrounding medium at controlled rates over a specified period. Encapsulated droplets are typically about 1 to 50 microns in diameter.
The enclosed liquid typically constitutes about 50 to 95% of the weight of the entire capsule, and may contain a small amount of solvent in addition to the active materials.
Encapsulated granules are characterized by porous membranes sealinq the openings of the granule carrier pores, trapping the liquid containing the active components inside for controlled release. A typical granule size ranges from 1 millimeter to 1 centimeter in diameter. In agricultural usage, the granule size is generally about 1 to 2 millimeters in diameter. Granules formed by extrusion, agglomeration, or prilling are useful in the present invention as well as materials in their naturally occurring form. Examples of such carriers are vermiculite, sintered clay granules, kaolin, attapulgite clay, sawdust, and granular carbon.
Useful encapsulating materials include natural and synthetic rubbers, cellulosic materials, styrene-butadiene copolymers, polyacrylonitriles, polyacrylates, polyesters, polyamides, polyurethanes, and starch xanthates.

E. IN GENERAL

Each of the above formulations can be prepared as a package containing the herbicide together with the other inqredients of the formulation (diluents, emulsifiers, surfactants, etc.). The formulations can also be prepared by a tank mix method, in which the ingredients are obtained separately and combined at the grower site.
In general, any conventional method of application can be used. The locus of application can be soil, seeds, seedlings, or the actual plants, as well as flooded fields. Post-emergent application is preferred. Dusts and liquid compositions can be applied by the use of powder dusters, boom and hand sprayers, and spray dusters. The compositions can also be applied from airplanes as dusts and sprays because they are effective in very low dosages. In order to modify or control the growth of germinating seeds or emerging seedlings, as a typical example, the dust and liquid compositions are applied to the soil according to conventional methods and are distributed in the soil to a depth of at least one-half inch below the soil surface. It is not necessary that the phytotoxic compositions be admixed with the soil particles. Instead, these compositions can be applied merely by spraying or sprinkling the surface of the soil. The phytotoxic compositions of this invention can also be applied by addition to irrigation water supplied to the field to be treated. This method of 5 application permits the penetration of the compositions into the soil as the water is absorbed therein. Dust compositions, granular compositions or liquid formulations applied to the surface of the soil can be distributed below the surface of the soil by conventional means such as discing, dragging or mixing operations.
) The herbicide compositions can also be applied to the soil through irrigation systems. According to this technique, the compositions are added directly to irrigation water immediately prior to irrigation of the field. This technique is applicable in all geographical areas regardless of rainfall, since it permits supplementation of the natural rainfall at critical stages of plant growth. In a typical application, the concentration of the herbicide composition in the irrigation water will range from about 10 to 150 parts per million by weight. The irriqa- tion water can be applied by the use of sprinkler systems, surface furrows, or flooding. Such application is most effectively done before the weeds germinate, either early in the spring prior to germination or within two days after cultivation of the field.
The amount of the present composition which constitutes a herbicidally effective amount depends upon the nature of the seeds or plants to be controlled. The rate of application of active ingredient varies fran about 0.01 to about 50 pounds per acre, preferably about 0.1 to about 25 pounds per acre with the actual amount depending on the overall cost and the desired results. It will be readily apparent to one skilled in the art that compositions exhibiting lower herbicidal activity will require a higher dosaqe than more active compounds for the same degree of control.

Claims

1. As new compounds, mixed alkylsulfonium salts of N-phosphonomethylglycine having the formula

wherein R¹ is selected from the group consisting of long-chain saturated or unsaturated alkyl groups having from 12 to 20 carbon atoms and R² and R₃ are the same or different and are selected from the group consisting of lower alkyl having from 1-3 carbon atoms.

2. The compound of Claim 1 in which R₁ is octadecyl and R₂ and R₃ are each methyl.

3. The compound of Claim 1 in which R¹ is hexadecyl and R₂ and R₃ are each methyl.

4. A method for the control of undesirable pests wich comprises applying to the locus where control is desired, a herbicidally effective amount of an N-phosphonomethylglcyine having the formula

5. The method of Claim 4 in which R¹ is octadecyl and R₂ and R₃ are each methyl.

6. The method of Claim 4 in which R¹ is hexadecyl and R₂ and R₃ are each methyl.

7. A herbicidal composition comprising a herbicidally effective amount of a compound according to Claim 1, and a diluent carrier.

1. A method for the control of undesirable pests which comprises applying to the locus where control is desired, a herbicidally effective amount of an N-phosphonomethylglycine having the formula:

wherein R¹ is selected from the group consisting of long-chain saturated or unsaturated alkyl groups having from 12 to 20 carbon atoms and R₂ and R₃ are the same or different and are selected from the group consisting of lower alkyl having from 1-3 carbon atoms.

2. A method as claimed in claim 1 in which R₁ is octadecyl and R₂ and R₃ are each methyl.

3. A method as claimed in claim 1 in which R₁ is hexadecyl and R₂ and R₃ are each methyl.

4. A herbicidal composition comprising a herbicidally effective amount of a compound as defined in any of claims 1 to 3.

5. A process for the preparation of compounds as defined in claim 1 in which N-phosphonomethylglycine is reacted with an appropriate alkylsulfonium halide in the presence of silver oxide, filtering off the insoluble silver halide precipitated as a consequence of the reaction, to leave the alkylsulfonium salt in solution.